Fungicidal mixtures

ABSTRACT

A fungicidal mixture containing 
     a) the oxime ether carboxamide of the formula I ##STR1##  and b) a morpholine or piperidine derivative II selected from the group of compounds IIa, IIb and IIc ##STR2##  in a synergistically active amount is described.

This is a Division of application Ser. No. 08/311,320 filed on Sep. 23,1994, now U.S. Pat. No. 5,472,963.

The present invention relates to a fungicidal mixture which contains

a) the oxime ether carboxamide of the formula I ##STR3## and b) amorpholine or piperidine derivative II selected from the group ofcompounds IIa, IIb and IIc ##STR4## in a synergistically active amount.

The invention additionally relates to processes for controlling harmfulfungi using mixtures of the compounds I and II and the use of thecompound I and a compound II for the production of mixtures of thistype.

The compound of the formula I, its preparation and its action againstharmful fungi are disclosed in the literature (EP-A 477 631).

The morpholine or piperidine derivatives II (IIa: common name:fenpropimorph, U.S. Pat. No. 4,202,894; IIb: common name: fenpropidin,U.S. Pat. No. 4,202,894; IIc: common name: tridemorph, DE-A 11 64 152),their preparation and their action against harmful fungi are likewiseknown.

With respect to a decrease in the application rates and an improvementof the spectrum of action of known compounds, the present invention isbased on mixtures which, with a reduced total amount of applied activecompounds, have an improved action against harmful fungi (synergisticmixtures).

Accordingly, the mixtures defined at the beginning have been found. Ithas additionally been found that on simultaneous joint or separateapplication of the compound I and a compound II or on application of thecompound I and a compound II in succession harmful fungi can becontrolled better than with the individual compounds.

The compound of the formula I can be present in the E or the Zconfiguration with respect to the C═X double bond (with respect to thecarboxylic acid function group). Accordingly, it can be used in themixture according to the invention in each case either as the pure E orZ isomer or as an E/Z isomer mixture. The E/Z isomer mixture or the Eisomer is preferably used, the E isomer being particularly preferred.

Because of the basic character of the NH groups, the compounds I and IIare able to form salts or adducts with inorganic or organic acids orwith metal ions.

Examples of inorganic acids are hydrohalic acids such as hydrofluoricacid, hydrochloric acid, hydrobromic acid and hydriodic acid, sulfuricacid, phosphoric acid and nitric acid.

Suitable organic acids are, for example, formic acid, carbonic acid andalkanoic acids such as acetic acid, trifluoroacetic acid,trichloroacetic acid and propionic acid and also glycolic acid,thiocyanic acid, lactic acid, succinic acid, citric acid, benzoic acid,cinnamic acid, oxalic acid, alkylsulfonic acids (sulfonic acids havingstraight-chain or branched alkyl radicals having 1 to 20 carbon atoms),arylsulfonic acids or -disulfonic acids (aromatic radicals such asphenyl and naphthyl which carry one or two sulfonic acid groups),alkylphosphonic acids (phosphonic acids containing straight-chain orbranched alkyl radicals having 1 to 20 carbon atoms), arylphosphonicacids or -diphosphonic acids (aromatic radicals such as phenyl andnaphthyl which carry one or two phosphoric acid radicals), the alkyl andaryl radicals being able to carry further substituents, e.g.p-toluenesulfonic acid, salicylic acid, p-aminosalicylic acid,2-phenoxybenzoic acid, 2-acetoxybenzoic acid etc.

Suitable metal ions are in particular the ions of the elements of thesecond main group, in particular calcium and magnesium, of the third andfourth main group, in particular aluminum, tin and lead, as well as ofthe first to eighth subgroup, in particular chromium, manganese, iron,cobalt, nickel, copper, zinc and others. The metal ions of the elementsof the subgroups of the fourth period are particularly preferred. Themetals can in this case be present in the different valencies applicableto them.

Preferably, the pure active compounds I and II are employed in thepreparation of the mixtures, to which, if required, further activecompounds against harmful fungi or other pests such as insects,arachnids or nematodes, or alternatively herbicidal or growth-regulatingactive compounds or fertilizers, can be admixed.

The mixtures of the compounds I and II and the simultaneous joint orseparate use of the compounds I and II are distinguished by anoutstanding action against a wide spectrum of phytopathogenic fungi, inparticular from the Ascomycetes and Basidiomycetes class. In some casesthey are systemically active and can therefore also be employed asfoliar and soil fungicides.

They have particular importance for the control of a multiplicity offungi on various crop plants such as cotton, vegetable plants (e.g.cucumbers, beans and cucurbits), barley, grass, oats, coffee, maize,fruit plants, rice, rye, soybean, grape, wheat, decorative plants, sugarcane and a multiplicity of seeds.

In particular, they are suitable for the control of the followingphytopathogenic fungi: Erysiphe graminis (powdery mildew) on cereals,Erysiphe cichoracearum and Sphaerotheca fuliginea on cucurbits,Podosphaera leucotricha on apples, Puccinia species on cereals,Rhizoctonia species on cotton and lawns, Ustilago species on cereals andsugar cane, Venturia inaequalis (scab) on apples, Helminthosporiumspecies on cereals, Septoria nodorum on wheat, Botrytis cinerea (graymold) on strawberries and vines, Cercospora arachidicola on groundnuts,Pseudocercosporella herpotrichoides on wheat and barley, Pyriculariaoryzae on rice, Phytophthora infestans on potatoes and tomatoes,Plasmopara viticola on vines, Alternaria species on vegetables and fruitand also Fusarium and Verticillium species.

They are additionally applicable in the protection of materials (e.g.wood preservation), for example against Paecilomyces variotii.

The compounds I and II can be applied simultaneously jointly orseparately, or in succession, the sequence in the case of separateapplication in general having no effect on the control success.

The compounds I and II are customarily applied in a weight ratio of from20:1 to 0.1:2, preferably from 10:1 to 0.2:1, in particular from 5:1 to0.5:1.

Depending on the type of effect desired, the application rates of themixtures according to the invention are from 0.01 to 0.5 kg/ha,preferably from 0.05 to 0.5 kg/ha, in particular from 0.05 to 0.3 kg/ha,for the compound I. The application rates for the compounds II arecorrespondingly from 0.05 to 1 kg/ha, preferably from 0.1 to 1 kg/ha, inparticular from 0.1 to 0.8 kg/ha.

In the treatment of seed, application rates of mixture of from 0.001 to50 g/kg of seed, preferably from 0.01 to 10 g/kg, in particular from0.01 to 5 g/kg, are in general used.

If harmful fungi which are pathogenic for plants are to be controlled,the separate or joint application of the compounds I and II or of themixtures of the compounds I and II is carried out by spraying or dustingthe seeds, the plants or the soil before or after sowing of the plantsor before or after emergence of the plants.

The fungicidal synergistic mixtures and the compounds I and II accordingto the invention can be prepared, for example, in the form of directlysprayable solutions, powders and suspensions or in the form ofhigh-percentage aqueous, oily or other suspensions, dispersions,emulsions, oil dispersions, pastes, dusting compositions, broadcastingcompositions or granules and applied by spraying, atomizing, dusting,broadcasting or watering. The application form is dependent on theintended use; it should in each case guarantee a dispersion of themixture according to the invention which is as fine and uniform aspossible.

The formulations are prepared in a manner known per se, e.g. by additionof solvents and/or carriers. Inert additives such as emulsifiers ordispersants are customarily admixed to the formulations.

Suitable surface-active substances are the alkali metal, alkaline earthmetal or ammonium salts of aromatic sulfonic acids, e.g. lignosulfonicacid, phenolsulfonic acid, naphthalenesulfonic acid anddibutylnaphthalenesulfonic acid, as well as of fatty acids, alkyl- andalkylarylsulfonates, alkyl-, lauryl ether and fatty alcohol sulfates,and also salts of sulfated hexa-, hepta- and octadecanols or fattyalcohol glycol ethers, condensation products of sulfonated naphthaleneand its derivatives with formaldehyde, condensation products ofnaphthalene or of naphthalenesulfonic acids with phenol andformaldehyde, polyoxyethylene octylphenol ethers, ethoxylated isooctyl-,octyl- or nonylphenol, alkylphenol or tributylphenyl polyglycol ethers,alkylaryl polyether alcohols, isotridecyl alcohol, fattyalcohol-ethylene oxide condensates, ethoxylated castor oil,polyoxyethylene or polyoxypropylene alkyl ethers, lauryl alcoholpolyglycol ether acetate, sorbitol esters, lignin-sulfite waste liquorsor methylcellulose.

Powder, broadcasting and dusting compositions can be prepared by mixingor joint grinding of the compounds I or II or the mixture of thecompounds I and II with a solid carrier.

Granules (e.g. coated, impregnated or homogeneous granules) arecustomarily prepared by binding the active compound or the activecompounds to a solid carrier.

Fillers or solid carriers used are, for example, mineral earths such assilica gel, silicic acids, silicates, talc, kaolin, limestone, lime,chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium andmagnesium sulfate, magnesium oxide, ground plastics, and fertilizerssuch as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureasand vegetable products such as cereal flour, tree bark meal, wood mealand nutshell meal, cellulose powder or other solid carriers.

The formulations in general contain from 0.1 to 95% by weight,preferably from 0.5 to 90% by weight, of one of the compounds I or II orthe mixture of the compounds I and II. The active com- pounds are inthis case employed in a purity of from 90% to 100%, preferably from 95%to 100% (according to NMR spectrum or HPLC).

The compounds I or II and the mixtures or the corresponding formulationsare applied by treating the harmful fungi, the plants, seeds, soils,surfaces, materials or spaces to be kept free from them with afungicidally active amount of the mixture, or of the compounds I and IIin the case of separate application. Application can be carried outbefore or after attack by the harmful fungi.

Examples of the synergistic action of the mixtures according to theinvention against harmful fungi.

It was possible to show the fungicidal action of the compounds and ofthe mixtures by the following tests:

The active compounds were prepared separately or jointly as a 20%strength emulsion in a mixture of 70% by weight of cyclohexanone, 20% byweight of Nekanil® LN (Lutensol® AP6, wetting agent having emulsifierand dispersant action based on ethoxylated alkylphenols) and 10% byweight of Emulphor® EL (Emulan® EL, emulsifier based on ethoxylatedfatty alcohols) and accordingly diluted to the desired concentrationwith water.

Assessment followed determination of the attacked leaf areas in percent.These percentage values were converted into degrees of action. Thedegrees of action of the active compound mixtures to be expected weredetermined according to the Colby formula R. S. Colby, Weeds 15, (1967)20-22! and compared with the degrees of action observed.

Colby formula:

    E=x+y-x×y/100

E is the degree of action to be expected, expressed in % of theuntreated control, when using the mixture of the active compounds A andB in the concentrations a and b

x is the degree of action, expressed in % of the untreated control, whenusing the active compound A in the concentration a

y is the degree of action, expressed in % of the untreated control, whenusing the active compound B in the concentration b

At a degree of action of 0, the attack of the treated plants correspondsto that of the untreated control plants; at a degree of action of 100the treated plants showed no attack.

Activity against Puccinia recondita (brown rust of wheat)

Leaves of wheat seedlings (Kanzler variety) were dusted with spores ofbrown rust (Puccinia recondita). The plants treated in this way wereincubated for 24 h at 20°-22° C. and a relative atmospheric humidity of90-95% and then treated with the aqueous active compound preparation.The extent of fungal development was determined after a further 8 daysat 20°-22° C. and 65-70% relative atmospheric humidity. Assessment wascarried out visually.

    ______________________________________                Application rate                             Degree of action  %!    Active compound                 ppm!        {observed/calculated}    ______________________________________    --          --           0    I           8            0    I           4            0    IIa         40           75    IIb         80           87    I + IIa     4 + 40       87/75    I + IIb     8 + 80       96/87    ______________________________________

From the results of the test it emerges that the degree of actionobserved in a mixture ratio of 1:10 is higher than the degree of actionforecast by the Colby formula.

We claim:
 1. A fungicidal mixture containing synergistic fungicidallyeffective amounts ofa) the oxime ether carboxamide of formula I ##STR5##and b) a morpholine compound of formula II ##STR6## wherein n=10-13 andcompounds a) and b) are present in a weight ratio of 20:1 to 0.1:2. 2.The fungicidal mixture of claim 1, wherein said weight ratio is 10:1 to0.2:1.
 3. The fungicidal mixture of claim 1, wherein said weight ratiois 5:1 to 0.5:1.
 4. A process for controlling harmful fungi, whichcomprises treating the harmful fungi, their environment or the plants,seeds, soils, surfaces, materials or spaces to be kept free from themwith synergistic fungicidally effective amounts of compound a) andcompound b) of claim
 1. 5. The process of claim 4, wherein compound a)and compound b) are applied simultaneously jointly or separately, or insuccession.
 6. The process of claim 4, wherein the harmful fungi, theirenvironment or the plants, seeds, soils, surfaces, materials or spacesto be kept free from them are treated with from 0.01-0.5 kg/ha ofcompound a).
 7. The process of claim 4, wherein the harmful fungi, theirenvironment or the plants, seeds, soils, surfaces, materials or spacesto be kept free from them are treated with from 0.05-1 kg/ha of compoundb).